Hydrogenation catalyst for maleic anhydride based on nickel-based ordered mesoporous silica-based material and preparation method thereof

Abstract

The application provides a maleic anhydride hydrogenation catalyst based on a nickel-based ordered mesoporous silicon-based material and a preparation method, the maleic anhydride hydrogenation catalyst comprising a nickel active component and a carrier, the carrier being an ordered mesoporous silicon-based material, and the nickel active component being loaded on the carrier in the form of an atomic layer. The maleic anhydride hydrogenation catalyst based on the nickel-based ordered mesoporous silicon-based material has good dispersion of active metal sites, a regular structure arrangement, is not easy to agglomerate and deactivate, has different pore diameters and specific surface areas under different preparation conditions, has few sites for adsorbing C=O bonds on the catalyst surface, has small side reactions, has good service life and high selectivity, and is suitable for large-scale popularization and application.

Description

Technical Field

[0001] This invention relates to the field of catalyst preparation technology, and in particular to a maleic anhydride hydrogenation catalyst based on nickel-based ordered mesoporous silica materials and its preparation method. Background Technology

[0002] Succinic anhydride, also known as succinic anhydride, is an important chemical raw material widely used in polymer materials, pharmaceuticals, agrochemicals, dyes, photographic chemicals, and fragrances. Its demand is increasing year by year, making it a valuable economic product. Maleic anhydride, or maleic monoxide, can be produced from n-butane through multi-step oxidation. It has a large production volume, mature technology, and ample supply. Therefore, the selective hydrogenation of maleic anhydride to produce succinic anhydride is the most common method in industrial production. However, the hydrogenation reaction of maleic anhydride, under different degrees of reaction, yields succinic anhydride or byproducts such as γ-butyrolactone and tetrahydrofuran, indicating the significant importance of developing maleic anhydride hydrogenation catalysts with high selectivity, mild operating conditions, and long lifespan.

[0003] CN106669745A discloses a catalyst for the hydrogenation of maleic anhydride to succinic anhydride and its preparation method. The preparation method of the catalyst includes the following steps: First, a porous ceramic is used as a support, and an aqueous solution of SnCl2 containing catechol is impregnated using an impregnation method. The pH of the SnCl2 aqueous solution containing catechol is 1.5-6; the mass concentration of catechol in the SnCl2 aqueous solution is 0.01-2%, and the mass concentration of tin chloride is 0.1-20 g / L. After impregnation, the ceramic is rinsed. Then, the rinsed porous ceramic is dipped into a palladium chloride solution, and after rinsing and drying, the catalyst for the liquid-phase hydrogenation of maleic anhydride is obtained. The catalyst prepared by this method has a strong interaction between the active component palladium and the acid-resistant porous ceramic support, the active component palladium is not easily lost, and the stability of the catalyst is greatly improved.

[0004] CN116474790A discloses a catalyst for the highly selective hydrogenation of maleic anhydride to succinic anhydride and its preparation. The catalyst consists of an active component and a support. The active component is highly dispersed on the support in an alloyed state through a complexing agent, and its amount is 1-30 wt% of the total catalyst weight, with the balance being the support. The catalyst has a specific surface area of ​​30-200 m². 2The catalyst has a surface acidity of 0.01-1.2 mmol NH3 / g and an average pore size of 9-30 nm, with pores of 10-20 nm accounting for 50-80% of the total pore size. The catalyst's performance is regulated by alloying the active components and controlling the combination of specific surface area, surface acidity, and pore diameter. This effectively improves the hydrogenation activity of maleic anhydride and the selectivity of succinic anhydride, achieving a selectivity greater than 99.999%, significantly reducing product separation costs, and achieving a purity meeting polymerization grade requirements.

[0005] CN115739111A discloses a catalyst and preparation method for the hydrogenation of maleic anhydride to prepare succinic anhydride, comprising the following steps: preparing a suspension by mixing aluminum hydroxide, aluminum oxide, an alkaline additive, and deionized water; obtaining powder A through liquid grinding, hydrothermal reaction, washing, filtration, and drying; preparing a binder solution B; placing powder A in the turntable of a ball rolling machine while simultaneously spraying solution B onto the turntable, rotating the ball to form particles; adding powder A while continuing to spray solution B until the raw material forms small balls of 2-5 mm; drying and calcining to obtain product C; preparing an active metal solution D; saturating product C with solution D, drying, and then saturating the product with solution D again before drying and calcining to obtain the catalyst.

[0006] However, the preparation cost of the above catalysts is relatively high and their catalytic activity needs to be further improved. Summary of the Invention

[0007] In view of the problems existing in the prior art, this invention provides a maleic anhydride hydrogenation catalyst based on nickel-based ordered mesoporous silica materials and its preparation method. Ordered mesoporous silica materials with different pore sizes and specific surface areas are synthesized via a hydrothermal method. These materials are then used as a support to synthesize nickel-based ordered mesoporous silica materials via atomic layer deposition (ALD) as a catalyst for the hydrogenation of maleic anhydride to succinic anhydride. The preparation method of this invention is simple to operate, and the obtained nickel-based ordered mesoporous silica material maleic anhydride hydrogenation catalyst exhibits good dispersion of active metal sites, a regular structural arrangement, is not prone to agglomeration and deactivation, has a long service life, and high selectivity.

[0008] To achieve this objective, the present invention adopts the following technical solution:

[0009] In a first aspect, the present invention provides a maleic anhydride hydrogenation catalyst based on a nickel-based ordered mesoporous silica material, the maleic anhydride hydrogenation catalyst comprising a nickel active component and a support, wherein the support is an ordered mesoporous silica material, and the nickel active component is loaded on the support in the form of atomic layers.

[0010] The maleic anhydride hydrogenation catalyst of this invention, based on a nickel-based ordered mesoporous silica material, supports Ni on an ordered mesoporous silica material with a high specific surface area and good dispersion of active species. This effectively improves the dispersion state of Ni centers and their interaction with the support, thereby enhancing the performance of the Ni-based catalyst. The maleic anhydride hydrogenation catalyst of this invention has few adsorption sites for C=O bonds on its surface, reducing the catalyst's hydrogenation activity for C=O bonds, inhibiting deep hydrogenation, and improving the selectivity of succinic anhydride.

[0011] When the nickel loading of the maleic anhydride hydrogenation catalyst based on nickel-based ordered mesoporous silica material described in this invention is low, it will result in too few active sites and poor reaction effect; when the nickel loading of the maleic anhydride hydrogenation catalyst based on nickel-based ordered mesoporous silica material described in this invention is high, it will cause nickel species to agglomerate during the reaction and the catalyst to deactivate rapidly.

[0012] Preferably, the specific surface area of ​​the carrier is 354–692 m². 2 / g, for example, could be 354m 2 / g、360m 2 / g、400m 2 / g、450m 2 / g、500m 2 / g、550m 2 / g or 692m 2 / g, etc., but not limited to the listed values; other unlisted values ​​within this range also apply.

[0013] The aperture is 4.2 to 7.9 nm, for example, it can be 4.2 nm, 4.5 nm, 5 nm, 5.5 nm, 6 nm, 7 nm or 7.9 nm, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0014] Preferably, the nickel loading in the maleic anhydride hydrogenation catalyst is 10-30 wt%, for example, it can be 10 wt%, 15 wt%, 18 wt%, 20 wt%, 25 wt%, 27 wt%, or 30 wt%, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable, preferably 10-20 wt%.

[0015] Secondly, the present invention also provides a method for preparing a maleic anhydride hydrogenation catalyst based on a nickel-based ordered mesoporous silica material as described in the first aspect, the preparation method comprising the following steps:

[0016] (1) Mix surfactant, water, inorganic acid, solvent and silicon reagent, and then perform static aging, solid-liquid separation and drying in sequence to obtain crude carrier product;

[0017] (2) After washing the crude carrier, the product is calcined to obtain an ordered mesoporous silicon-based material;

[0018] (3) Using tetramethylethylenediamine diacetylacetone nickel as a precursor, atomic layer deposition is performed on the ordered mesoporous silicon-based material to obtain the maleic anhydride hydrogenation catalyst based on nickel-based ordered mesoporous silicon-based material.

[0019] The maleic anhydride hydrogenation catalyst based on nickel-based ordered mesoporous silica materials described in this invention uses a support synthesized via a hydrothermal method. The internal tension during silicon species formation can be adjusted by changing the acidity of the reaction solution or the solvent, thereby controlling the specific surface area and pore size of the final support. Simultaneously, nickel active centers are loaded using atomic layer deposition (ALD), uniformly dispersing the active metal sites on the support surface by loading single atoms layer by layer. This improves the selectivity of the maleic anhydride hydrogenation catalyst based on nickel-based ordered mesoporous silica materials for succinic anhydride hydrogenation. The preparation method described in this invention is simple to operate, has low preparation cost, and produces a maleic anhydride hydrogenation catalyst with a long service life and high selectivity.

[0020] The water described in this invention includes deionized water.

[0021] Preferably, the mixture of surfactant, water, inorganic acid, solvent and silicon reagent in step (1) is carried out in a hydrothermal reactor.

[0022] Preferably, the specific order of mixing the surfactant, water, inorganic acid, solvent and silicon reagent is as follows: first mix the surfactant and water, then add the inorganic acid to adjust the acidity, and continue stirring until the surfactant is completely dissolved; then add the solvent and perform a first heat preservation and stirring treatment; after the solution is clear, add the silicon reagent and perform a second heat preservation and stirring treatment.

[0023] Preferably, the temperature of the mixed surfactant and water is 25 to 60°C, for example, it can be 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C or 60°C, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable, preferably 30 to 50°C.

[0024] Preferably, the time for the first heat preservation and stirring treatment is 0.8 to 1.2 hours, for example, it can be 0.8 hours, 0.9 hours, 1 hour, 1.05 hours, 1.08 hours, 1.1 hours, 1.15 hours or 1.2 hours, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable, preferably 0.9 to 1.1 hours.

[0025] Preferably, the second heat preservation and stirring time is 12 to 48 hours, for example, it can be 12 hours, 15 hours, 18 hours, 20 hours, 25 hours, 30 hours, 40 hours or 48 hours, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable, preferably 24 to 36 hours.

[0026] Preferably, the surfactant comprises a polyoxypropylene-polyoxyethylene copolymer.

[0027] Preferably, the inorganic acid includes hydrochloric acid with a concentration of 10 to 35 wt%, such as 10 wt%, 15 wt%, 20 wt%, 25 wt%, 27 wt%, 30 wt%, or 35 wt%, but is not limited to the listed values; other unlisted values ​​within this range are also applicable.

[0028] Alternatively, the solvent may be nitric acid with a concentration of 5–10 wt%, for example, 5 wt%, 5.5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, or 10 wt%, but is not limited to the listed values; other unlisted values ​​within this range are also applicable. Preferably, the solvent comprises any one or a combination of at least two of n-butanol, toluene, acetonitrile, or tetrahydrofuran, wherein typical but not limiting combinations include a combination of n-butanol and toluene, a combination of acetonitrile and tetrahydrofuran, or a combination of n-butanol and acetonitrile or tetrahydrofuran and toluene.

[0029] By selecting solvents with different polarities, this invention can influence the interaction between silicon species and templates, thereby regulating the internal structure of the support.

[0030] Preferably, the silicon reagent comprises sodium silicate and / or tetraethyl orthosilicate.

[0031] Preferably, the molar ratio of the surfactant, water, inorganic acid, solvent, and silicon reagent is (0.1-0.5):(50-250):(0.5-1.5):(1.1-2), for example, it can be 0.1:50:0.5:1.1, 0.2:55:0.6:1.13, 0.2:70:0.7:1.19, 0.3:90:1:1.3, 0.35:100:1.2:1.5, 0.4:150:1.5:1.7, or 0.5:250:1.5:2, etc., but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable, preferably (0.2-0.4):(90-150):(0.8-1.3):(1.05-1.5).

[0032] In this invention, the amount of inorganic acid and the type of solvent are crucial. By changing the acidity of the reaction solution or the solvent, the internal tension during silicon species formation can be adjusted, thereby controlling the specific surface area and pore size of the final carrier. When the amount of inorganic acid is too small, the solution acidity is too weak, making it difficult for silicon species to form a stable structure. When the amount of inorganic acid is too large, there are too many acidic sites on the surface of the formed silicon species, inducing an overreaction, namely the hydrogenation of succinic anhydride to form γ-butyrolactone.

[0033] Preferably, the static aging temperature in step (1) is 60 to 150°C, for example, it can be 60°C, 70°C, 90°C, 100°C, 110°C, 120°C, 140°C or 150°C, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable, preferably 70 to 120°C.

[0034] Preferably, the static aging time is 12 to 48 hours, for example, it can be 12 hours, 18 hours, 20 hours, 30 hours, 35 hours, 40 hours, 45 hours or 48 hours, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable, preferably 24 to 36 hours.

[0035] Preferably, the drying temperature is 80-120°C, for example, it can be 80°C, 85°C, 90°C, 100°C, 110°C, 115°C, 118°C or 120°C, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable, preferably 90-110°C.

[0036] Preferably, the drying time is 12 to 48 hours, for example, it can be 12 hours, 18 hours, 20 hours, 30 hours, 35 hours, 40 hours, 45 hours or 48 hours, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable, preferably 24 to 36 hours.

[0037] Preferably, the washing solution used in step (2) includes ethanol and dilute hydrochloric acid.

[0038] Preferably, the number of washing cycles is 2 to 5, for example, 2, 3, 4 or 5 times.

[0039] Preferably, the washing steps consist of first performing 2 to 5 ethanol washes followed by 2 to 5 dilute hydrochloric acid washes.

[0040] Preferably, the calcination temperature is 450–700°C, for example, 450°C, 480°C, 500°C, 510°C, 550°C, 600°C, 650°C, or 700°C, but is not limited to the listed values. Other unlisted values ​​within this range are also applicable, with 550–600°C being the preferred temperature.

[0041] Preferably, the roasting time is 8 to 15 hours, for example, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours or 15 hours, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable, preferably 9 to 12 hours.

[0042] Preferably, the atomic layer deposition in step (3) is carried out in an atomic layer deposition reactor.

[0043] Preferably, the specific process of atomic layer deposition is as follows: using tetramethylethylenediamine diacetylacetone nickel as a precursor, after pulse adsorption of the ordered mesoporous silica-based material, the material is sequentially subjected to a first nitrogen purging, ozone oxidation, and a second nitrogen purging. The pulse adsorption, first nitrogen purging, ozone oxidation, and second nitrogen purging are repeated in a cycle to obtain the maleic anhydride hydrogenation catalyst based on nickel-based ordered mesoporous silica-based material.

[0044] Preferably, the temperature for atomic layer deposition is 150°C to 500°C, for example, it can be 150°C, 160°C, 200°C, 250°C, 300°C, 400°C or 500°C, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable, preferably 200°C to 450°C.

[0045] Preferably, the pulse adsorption time in a single cycle is 5 to 15 seconds, for example, 5 seconds, 6 seconds, 7 seconds, 8 seconds, 10 seconds, 13 seconds, or 15 seconds, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable, preferably 8 to 12 seconds.

[0046] Preferably, the first nitrogen purging time is 10 to 30 seconds, for example, it can be 10 seconds, 12 seconds, 15 seconds, 20 seconds, 22 seconds, 25 seconds or 30 seconds, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable, preferably 12 to 24 seconds.

[0047] Preferably, the volume concentration of ozone is 5-10%, for example, it can be 5%, 6%, 7%, 8%, 8.5%, 9% or 10%, etc., but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable, preferably 7-8%.

[0048] Preferably, the ozone oxidation time is 10 to 30 seconds, for example, 10 seconds, 12 seconds, 15 seconds, 20 seconds, 22 seconds, 25 seconds or 30 seconds, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable, preferably 12 to 24 seconds.

[0049] Preferably, the first nitrogen purging time is 10 to 30 seconds, for example, it can be 10 seconds, 12 seconds, 15 seconds, 20 seconds, 22 seconds, 25 seconds or 30 seconds, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable, preferably 12 to 24 seconds.

[0050] Preferably, the number of cycles is 10 to 20, for example, 10, 12, 13, 15, 17, 18 or 20 times, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable, preferably 12 to 18 times.

[0051] There are no limitations on the solid-liquid separation described in this invention. Any method known to those skilled in the art for solid-liquid separation can be used, such as filtration, sedimentation, or centrifugation.

[0052] As a preferred technical solution of the present invention, the preparation method includes the following steps:

[0053] (1) In a hydrothermal reactor, at a temperature of 25-60℃, the surfactant and water are first mixed, and then an inorganic acid is added to adjust the acidity. The mixture is stirred continuously until the surfactant is completely dissolved. Then, the solvent is added and a first heat preservation and stirring treatment is carried out for 0.8-1.2h. After the solution is clear, a silicon reagent is added and a second heat preservation and stirring treatment is carried out for 12-48h. Then, the mixture is subjected to static aging at a temperature of 60-150℃ for 12-48h, solid-liquid separation, and drying at a temperature of 80-120℃ for 12-48h to obtain the crude carrier.

[0054] The surfactant comprises a polyoxypropylene-polyoxyethylene copolymer; the inorganic acid comprises hydrochloric acid with a concentration of 10-35 wt% or nitric acid with a concentration of 5-10 wt%; the solvent comprises any one or a combination of at least two of n-butanol, toluene, acetonitrile, or tetrahydrofuran; the silicon reagent comprises sodium silicate and / or tetraethyl orthosilicate; the molar ratio of the surfactant, water, inorganic acid, solvent, and silicon reagent is (0.1-0.5):(50-250):(0.5-1.5):(1.1-2);

[0055] (2) The crude carrier is first washed with ethanol 2 to 5 times and then washed with dilute hydrochloric acid 2 to 5 times, and then calcined at a temperature of 450 to 700°C for 8 to 15 hours to obtain an ordered mesoporous silicon-based material.

[0056] (3) In an atomic layer deposition reactor, at a temperature of 150℃~500℃, using tetramethylethylenediamine diacetylacetone nickel as a precursor, after pulse adsorption of the ordered mesoporous silica-based material for 5~15s, the material is sequentially subjected to a first nitrogen purging for 10~30s, ozone oxidation with a volume concentration of 5~10% for 10~30s, and a second nitrogen purging for 10~30s. This process is repeated 10~20 times for pulse adsorption, first nitrogen purging, ozone oxidation, and second nitrogen purging to obtain the maleic anhydride hydrogenation catalyst based on nickel-based ordered mesoporous silica-based material.

[0057] Thirdly, the present invention also provides the use of the maleic anhydride hydrogenation catalyst based on nickel-based ordered mesoporous silica material described in the first aspect, characterized in that the maleic anhydride hydrogenation catalyst based on nickel-based ordered mesoporous silica material is used to catalyze the hydrogenation of maleic anhydride reaction solution to produce succinic anhydride.

[0058] Preferably, the maleic anhydride hydrogenation catalyst is reduced in a hydrogen atmosphere before use, and the reduction temperature is 300-800°C, for example, 300°C, 350°C, 400°C, 500°C, 600°C, 700°C or 800°C, but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0059] Preferably, the mass concentration of the maleic anhydride reaction solution is 5-20%, for example, it can be 5%, 8%, 10%, 12%, 15%, 18% or 20%, etc., but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0060] Preferably, the mass hourly space velocity (MSV) of the maleic anhydride reaction solution is 0.5–2 h⁻¹. -1 For example, it could be 0.5h -1 0.7h -1 0.9h -1 1h -1 1.1h -1 1.4h -1 1.5h -1 or 2h -1 This applies to, but is not limited to, the listed values; other unlisted values ​​within this range also apply.

[0061] Preferably, tetrahydrofuran is used as a solvent in the process of hydrogenating maleic anhydride reaction solution to produce succinic anhydride.

[0062] Preferably, the temperature for hydrogenating maleic anhydride reaction solution to produce succinic anhydride is 70–150°C, for example, 70°C, 80°C, 90°C, 100°C, 120°C, 140°C, or 150°C, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable, with 90–120°C being the preferred temperature.

[0063] Preferably, the pressure at which the maleic anhydride reaction solution is hydrogenated to produce succinic anhydride is 1.0 to 3.0 MPa, for example, it can be 1.0 MPa, 1.5 MPa, 1.8 MPa, 2.0 MPa, 2.5 MPa, 2.8 MPa or 3.0 MPa, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable, preferably 2.0 to 3.0 MPa.

[0064] Preferably, the hydrogen-to-anhydride ratio in the hydrogenation reaction solution to produce succinic anhydride is 5:1 to 20:1, for example, it can be 5:1, 8:1, 10:1, 15:1, 18:1, 19:1 or 20:1, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0065] Compared with the prior art, the present invention has at least the following beneficial effects:

[0066] (1) The maleic anhydride hydrogenation catalyst based on nickel-based ordered mesoporous silica material provided by the present invention has good dispersion of active metal sites, regular structure arrangement, and is not easy to agglomerate and deactivate. It has different pore size and specific surface area under different preparation conditions. There are few sites for adsorbing C=O bonds on the catalyst surface and small side reactions. The maleic anhydride hydrogenation catalyst based on nickel-based ordered mesoporous silica material has good service life and high selectivity.

[0067] (2) The preparation method of maleic anhydride hydrogenation catalyst based on nickel-based ordered mesoporous silica material provided by the present invention is simple to operate and suitable for industrial production. Attached Figure Description

[0068] Figure 1 This is an HR-TEM image of carrier-1 obtained in Embodiment 1 of the present invention.

[0069] Figure 2 This is an HR-TEM image of maleic anhydride hydrogenation catalyst C1 based on nickel-based ordered mesoporous silica material obtained in Example 1 of the present invention. Detailed Implementation

[0070] The technical solution of the present invention will be further described below with reference to the accompanying drawings and specific embodiments.

[0071] The present invention will now be described in further detail. However, the examples described below are merely simplified examples of the present invention and do not represent or limit the scope of protection of the present invention. The scope of protection of the present invention is determined by the claims.

[0072] Example 1

[0073] This embodiment provides a method for preparing a maleic anhydride hydrogenation catalyst based on a nickel-based ordered mesoporous silica material, the preparation method comprising the following steps:

[0074] (1) In a hydrothermal reactor, at a temperature of 25°C, 3.32 g of surfactant polyoxypropylene-polyoxyethylene copolymer and 180 g of deionized water were mixed. Then, 4.2 mL of 35 wt% hydrochloric acid was added to adjust the acidity, and the mixture was stirred continuously until the surfactant was completely dissolved. After that, 9.63 g of n-butanol was added and the mixture was subjected to a first heat treatment and stirring for 1.2 h. After the solution became clear, 20.83 g of tetraethyl orthosilicate was added and the mixture was subjected to a second heat treatment and stirring for 36 h. After that, the mixture was subjected to static aging at 90°C for 36 h, filtration, and drying at 120°C for 36 h to obtain the crude carrier product.

[0075] (2) The crude carrier is first washed with ethanol three times and then washed with dilute hydrochloric acid three times, and then calcined at 500℃ for 12 hours to obtain carrier-1.

[0076] (3) In an atomic layer deposition reactor at a temperature of 200°C, using tetramethylethylenediamine diacetylacetone nickel as a precursor, after pulse adsorption of the carrier-1 for 12s, the catalyst is sequentially subjected to a first nitrogen purging for 12s, ozone oxidation with a volume concentration of 7% for 10s, and a second nitrogen purging for 10s. The pulse adsorption, first nitrogen purging, ozone oxidation, and second nitrogen purging are repeated 10 times to obtain the maleic anhydride hydrogenation catalyst based on nickel-based ordered mesoporous silica material.

[0077] In this embodiment, the total amount of the support is 45.02g, and the total amount of nickel tetramethylethylenediamine diacetylacetone used is 50.31g. The resulting catalyst is called C1 (10% Ni).

[0078] The HR-TEM image of carrier-1 obtained in this embodiment is as follows: Figure 1 As shown, from Figure 1 It can be seen that a uniform pore structure is formed inside the carrier, and the pores are interconnected.

[0079] The HR-TEM image of the maleic anhydride hydrogenation catalyst C1 based on nickel-based ordered mesoporous silica material obtained in this embodiment is as follows: Figure 2 As shown, from Figure 2 It can be seen that the active metal atoms are uniformly loaded on the pores inside the support.

[0080] Example 2

[0081] This embodiment provides a method for preparing a maleic anhydride hydrogenation catalyst based on a nickel-based ordered mesoporous silica material, the preparation method comprising the following steps:

[0082] (1) In a hydrothermal reactor, at a temperature of 35°C, 6.61g of surfactant polyoxypropylene-polyoxyethylene copolymer and 180g of deionized water were mixed. Then, 11.6mL of 25wt% hydrochloric acid was added to adjust the acidity, and the mixture was stirred continuously until the surfactant was completely dissolved. After that, 10.13g of toluene was added and the mixture was subjected to a first heat treatment and stirring for 1h. After the solution became clear, 20.81g of tetraethyl orthosilicate was added and the mixture was subjected to a second heat treatment and stirring for 12h. After that, the mixture was subjected to static aging at 150°C for 12h, filtration, and drying at 100°C for 12h to obtain the crude carrier product.

[0083] (2) The crude carrier is first washed twice with ethanol and then twice with dilute hydrochloric acid, and then calcined at 550°C for 8 hours to obtain carrier-2.

[0084] (3) In an atomic layer deposition reactor at a temperature of 300°C, using tetramethylethylenediamine diacetylacetone nickel as a precursor, after pulse adsorption of the carrier-2 for 12s, the catalyst is sequentially subjected to a first nitrogen purging for 30s, ozone oxidation with a volume concentration of 5% for 30s, and a second nitrogen purging for 30s. The pulse adsorption, first nitrogen purging, ozone oxidation, and second nitrogen purging are repeated 15 times to obtain the maleic anhydride hydrogenation catalyst based on nickel-based ordered mesoporous silica material.

[0085] In this embodiment, the total amount of the support is 45.07g, and the total amount of tetramethylethylenediamine diacetylacetone nickel used is 50.30g. The resulting catalyst is called C2 (10% Ni).

[0086] Example 3

[0087] This embodiment provides a method for preparing a maleic anhydride hydrogenation catalyst based on a nickel-based ordered mesoporous silica material, the preparation method comprising the following steps:

[0088] (1) In a hydrothermal reactor, at a temperature of 35°C, 4.98g of surfactant polyoxypropylene-polyoxyethylene copolymer and 180g of deionized water were mixed. 72.81mL of 5wt% nitric acid was added to adjust the acidity, and the mixture was stirred continuously until the surfactant was completely dissolved. Then, 5.34g of acetonitrile was added and the mixture was subjected to a first heat treatment and stirring for 1h. After the solution became clear, 20.82g of tetraethyl orthosilicate was added and the mixture was subjected to a second heat treatment and stirring for 24h. After that, the mixture was subjected to static aging at 110°C for 24h, filtration, and drying at 110°C for 24h to obtain the crude carrier product.

[0089] (2) The crude carrier is first washed with ethanol 5 times and then washed with dilute hydrochloric acid 5 times, and then calcined at 550℃ for 10h to obtain carrier-3.

[0090] (3) In an atomic layer deposition reactor at a temperature of 350°C, using tetramethylethylenediamine diacetylacetone nickel as a precursor, after pulse adsorption of the carrier-3 for 10s, the catalyst is sequentially subjected to a first nitrogen purging for 10s, ozone oxidation with a volume concentration of 7% for 15s, and a second nitrogen purging for 15s. The pulse adsorption, first nitrogen purging, ozone oxidation, and second nitrogen purging are repeated 15 times to obtain the maleic anhydride hydrogenation catalyst based on nickel-based ordered mesoporous silica material.

[0091] In this embodiment, the total amount of the support is 45.01g, and the total amount of tetramethylethylenediamine diacetylacetone nickel used is 50.33g. The resulting catalyst is called C3 (10% Ni).

[0092] Example 4

[0093] This embodiment provides a method for preparing a maleic anhydride hydrogenation catalyst based on a nickel-based ordered mesoporous silica material, the preparation method comprising the following steps:

[0094] (1) In a hydrothermal reactor, at a temperature of 60°C, 16.54 g of surfactant polyoxypropylene-polyoxyethylene copolymer and 450 g of deionized water were mixed. Then, 43.75 mL of 10 wt% hydrochloric acid was added to adjust the acidity, and the mixture was stirred continuously until the surfactant was completely dissolved. After that, 14.8 g of n-butanol was added and the mixture was subjected to a first heat preservation and stirring treatment for 0.8 h. After the solution became clear, 20.84 g of tetraethyl orthosilicate was added and the mixture was subjected to a second heat preservation and stirring treatment for 48 h. After that, the mixture was subjected to static aging at a temperature of 60°C for 48 h, filtration, and drying at a temperature of 100°C for 48 h to obtain the crude carrier product.

[0095] (2) The crude carrier is first washed with ethanol three times and then washed with dilute hydrochloric acid three times, and then calcined at 700℃ for 15 hours to obtain carrier-4.

[0096] (3) In an atomic layer deposition reactor at a temperature of 480°C, using tetramethylethylenediamine diacetylacetone nickel as a precursor, after pulse adsorption of the carrier-4 for 12s, the catalyst is sequentially subjected to a first nitrogen purging for 10s, ozone oxidation with a volume concentration of 10% for 10s, and a second nitrogen purging for 15s. The pulse adsorption, first nitrogen purging, ozone oxidation, and second nitrogen purging are repeated 12 times to obtain the maleic anhydride hydrogenation catalyst based on nickel-based ordered mesoporous silica material.

[0097] In this embodiment, the total amount of the support is 45.01g, and the total amount of tetramethylethylenediamine diacetylacetone nickel used is 50.28g. The resulting catalyst is called C4 (10% Ni).

[0098] Example 5

[0099] This embodiment provides a method for preparing a maleic anhydride hydrogenation catalyst based on a nickel-based ordered mesoporous silica material, the preparation method comprising the following steps:

[0100] (1) In a hydrothermal reactor, at a temperature of 45°C, 4.95g of surfactant polyoxypropylene-polyoxyethylene copolymer and 198g of deionized water were mixed. Then, 11.73mL of 20wt% hydrochloric acid was added to adjust the acidity, and the mixture was stirred continuously until the surfactant was completely dissolved. After that, 11.10g of tetrahydrofuran was added and the mixture was subjected to a first heat preservation and stirring treatment for 1.2h. After the solution became clear, 12.07g of sodium silicate was added and the mixture was subjected to a second heat preservation and stirring treatment for 24h. After that, the mixture was subjected to static aging at 100°C for 24h, filtration, and drying at 90°C for 24h to obtain the crude carrier product.

[0101] (2) The crude carrier is first washed twice with ethanol and then twice with dilute hydrochloric acid, and then calcined at 550°C for 10 hours to obtain carrier-5.

[0102] (3) In an atomic layer deposition reactor at a temperature of 250°C, using tetramethylethylenediamine diacetylacetone nickel as a precursor, after pulse adsorption of the carrier-5 for 10s, the catalyst is sequentially subjected to a first nitrogen purging for 20s, ozone oxidation with a volume concentration of 7% for 12s, and a second nitrogen purging for 20s. The pulse adsorption, first nitrogen purging, ozone oxidation, and second nitrogen purging are repeated 15 times to obtain the maleic anhydride hydrogenation catalyst based on nickel-based ordered mesoporous silica material.

[0103] In this embodiment, the total amount of the support is 44.95g, and the total amount of tetramethylethylenediamine diacetylacetone nickel used is 50.38g. The resulting catalyst is called C5 (10% Ni).

[0104] Example 6

[0105] This embodiment provides a method for preparing a maleic anhydride hydrogenation catalyst based on a nickel-based ordered mesoporous silica material, the preparation method comprising the following steps:

[0106] (1) In a hydrothermal reactor, at a temperature of 55°C, 9.88g of surfactant polyoxypropylene-polyoxyethylene copolymer and 180g of deionized water were mixed. Then, 21.52mL of 10wt% nitric acid was added to adjust the acidity, and the mixture was stirred continuously until the surfactant was completely dissolved. After that, 9.62g of n-butanol was added and the mixture was subjected to a first heat treatment and stirring for 1h. After the solution became clear, 12.05g of sodium silicate was added and the mixture was subjected to a second heat treatment and stirring for 36h. After that, the mixture was subjected to static aging at 60°C for 36h, filtration, and drying at 80°C for 36h to obtain the crude carrier product.

[0107] (2) The crude carrier is first washed with ethanol three times and then washed with dilute hydrochloric acid three times, and then calcined at 450°C for 8 hours to obtain carrier-6.

[0108] (3) In an atomic layer deposition reactor at a temperature of 500°C, using tetramethylethylenediamine diacetylacetone nickel as a precursor, after pulse adsorption of the carrier-6 for 12s, the catalyst is sequentially subjected to a first nitrogen purging for 30s, ozone oxidation with a volume concentration of 7% for 15s, and a second nitrogen purging for 30s. The pulse adsorption, first nitrogen purging, ozone oxidation, and second nitrogen purging are repeated 12 times to obtain the maleic anhydride hydrogenation catalyst based on nickel-based ordered mesoporous silica material.

[0109] In this embodiment, the total amount of the support is 44.97g, and the total amount of nickel tetramethylethylenediamine diacetylacetone used is 50.30g. The resulting catalyst is called C6 (10% Ni).

[0110] Example 7

[0111] This embodiment provides a method for preparing a maleic anhydride hydrogenation catalyst based on a nickel-based ordered mesoporous silica material, the preparation method comprising the following steps:

[0112] (1) In a hydrothermal reactor, at a temperature of 35°C, 3.32 g of surfactant polyoxypropylene-polyoxyethylene copolymer and 90 g of deionized water were mixed. Then, 10.4 mL of 35 wt% hydrochloric acid was added to adjust the acidity, and the mixture was stirred continuously until the surfactant was completely dissolved. After that, 8.20 g of n-butanol was added and the mixture was subjected to a first heat treatment and stirring for 1 h. After the solution became clear, 12.08 g of sodium silicate was added and the mixture was subjected to a second heat treatment and stirring for 24 h. After that, the mixture was subjected to a static aging at 110°C for 24 h, filtration, and drying at 110°C for 24 h to obtain the crude carrier product.

[0113] (2) The crude carrier is first washed with ethanol three times and then washed with dilute hydrochloric acid three times, and then calcined at 600℃ for 10h to obtain carrier-7.

[0114] (3) In an atomic layer deposition reactor at a temperature of 280°C, using tetramethylethylenediamine diacetylacetone nickel as a precursor, after pulse adsorption of the carrier-7 for 5s, the catalyst is sequentially subjected to a first nitrogen purging for 10s, ozone oxidation with a volume concentration of 7% for 10s, and a second nitrogen purging for 10s. The pulse adsorption, first nitrogen purging, ozone oxidation, and second nitrogen purging are repeated 10 times to obtain the maleic anhydride hydrogenation catalyst based on nickel-based ordered mesoporous silica material.

[0115] In this embodiment, the total amount of the support is 45.04 g, and the total amount of nickel tetramethylethylenediamine diacetylacetone used is 50.39 g. The resulting catalyst is called C7 (10% Ni).

[0116] Example 8

[0117] This embodiment provides a method for preparing a maleic anhydride hydrogenation catalyst based on a nickel-based ordered mesoporous silica material, the preparation method comprising the following steps:

[0118] (1) In a hydrothermal reactor, at a temperature of 35°C, 6.62g of surfactant polyoxypropylene-polyoxyethylene copolymer and 168g of deionized water were mixed. Then, 14.48mL of 30wt% hydrochloric acid was added to adjust the acidity, and the mixture was stirred continuously until the surfactant was completely dissolved. After that, 11.95g of toluene was added and the mixture was subjected to a first heat preservation and stirring treatment for 1h. After the solution became clear, 12.08g of sodium silicate was added and the mixture was subjected to a second heat preservation and stirring treatment for 12h. After that, the mixture was subjected to static aging at 120°C for 12h, filtration, and drying at 100°C for 12h to obtain the crude carrier product.

[0119] (2) The crude carrier is first washed with ethanol 4 times and then washed with dilute hydrochloric acid 4 times, and then calcined at 700℃ for 12h to obtain carrier-8.

[0120] (3) In an atomic layer deposition reactor at a temperature of 300°C, using tetramethylethylenediamine diacetylacetone nickel as a precursor, after pulse adsorption of the carrier-8 for 12s, the catalyst is sequentially subjected to a first nitrogen purging for 18s, ozone oxidation with a volume concentration of 7% for 12s, and a second nitrogen purging for 18s. After 15 cycles of pulse adsorption, first nitrogen purging, ozone oxidation, and second nitrogen purging, the maleic anhydride hydrogenation catalyst based on nickel-based ordered mesoporous silica material can be obtained.

[0121] In this embodiment, the total amount of the support is 45.05g, and the total amount of tetramethylethylenediamine diacetylacetone nickel used is 50.33g. The resulting catalyst is called C8 (10% Ni).

[0122] Example 9

[0123] This embodiment provides a method for preparing a maleic anhydride hydrogenation catalyst based on nickel-based ordered mesoporous silica materials. The preparation method is the same as in Example 1 except that step (3) is replaced by “in an atomic layer deposition reactor at a temperature of 160°C, using tetramethylethylenediamine diacetylacetone nickel as a precursor, after pulse adsorption of the carrier-1 for 5s, the first nitrogen purging for 10s, ozone oxidation with a volume concentration of 7% for 15s, and the second nitrogen purging for 15s are performed sequentially, and the pulse adsorption, first nitrogen purging, ozone oxidation, and second nitrogen purging are repeated 12 times”.

[0124] In this embodiment, the total amount of the support is 44.99g, and the total amount of nickel tetramethylethylenediamine diacetylacetone used is 100.78g. The resulting catalyst is called C1-2 (20% Ni).

[0125] Example 10

[0126] This embodiment provides a method for preparing a maleic anhydride hydrogenation catalyst based on nickel-based ordered mesoporous silica materials. The preparation method is the same as in Example 1 except that step (3) is replaced by “in an atomic layer deposition reactor at a temperature of 150°C, using tetramethylethylenediamine diacetylacetone nickel as a precursor, after pulse adsorption of the carrier-1 for 15s, the first nitrogen purging for 24s, ozone oxidation with a volume concentration of 10% for 24s, and the second nitrogen purging for 30s are performed sequentially, and the pulse adsorption, first nitrogen purging, ozone oxidation and second nitrogen purging are repeated 20 times”.

[0127] In this embodiment, the total amount of the support is 45.05g, and the total amount of nickel tetramethylethylenediamine diacetylacetone used is 150.88g. The resulting catalyst is called C1-3 (30% Ni).

[0128] Example 11

[0129] This embodiment provides a method for preparing a maleic anhydride hydrogenation catalyst based on nickel-based ordered mesoporous silica material. The preparation method is the same as in Example 1, except that in step (1) 2.1 mL of 35 wt% hydrochloric acid is added.

[0130] Example 12

[0131] This embodiment provides a method for preparing a maleic anhydride hydrogenation catalyst based on nickel-based ordered mesoporous silica material. The preparation method is the same as in Example 1 except for step (1) where 21.0 mL of 35 wt% hydrochloric acid is added.

[0132] Example 13

[0133] This embodiment provides a method for preparing a maleic anhydride hydrogenation catalyst based on nickel-based ordered mesoporous silica materials. The preparation method is the same as in Example 1, except that in step (1), the solvent n-butanol is replaced with diethyl ether.

[0134] Comparative Example 1

[0135] This comparative example provides a method for preparing a maleic anhydride hydrogenation catalyst based on a nickel-based ordered mesoporous silica material. The preparation method is the same as in Example 1, except that step (3) is replaced by "adding 24.55g of nickel nitrate and 200mL of deionized water to a beaker, and after complete dissolution, adding 45.02g of the above-mentioned support-1, and impregnating at room temperature for 1 hour. The resulting sample is aged at 90°C for 12 hours, filtered while hot, and calcined at 350°C for 16 hours".

[0136] The catalyst obtained in this comparative example is called C-jz (10% Ni).

[0137] Comparative Example 2

[0138] This comparative example provides a method for preparing a maleic anhydride hydrogenation catalyst based on nickel-based ordered mesoporous silica material. The preparation method is the same as in Example 1, except that the total amount of nickel used in the atomic layer deposition of step (3) is 25.12 g and the nickel loading of the obtained catalyst is 5 wt%.

[0139] The catalyst obtained in this comparative example is called C. Ni5 (5% Ni).

[0140] Comparative Example 3

[0141] This comparative example provides a method for preparing a maleic anhydride hydrogenation catalyst based on nickel-based ordered mesoporous silica material. The preparation method is the same as in Example 1, except that the total amount of nickel used in the atomic layer deposition of step (3) is 176.52 g and the nickel loading of the obtained catalyst is 35 wt%.

[0142] The catalyst obtained in this comparative example is called C. Ni35 (35% Ni).

[0143] The pore size and specific surface area of ​​the carriers-1 to-8 obtained in Examples 1 to 8 above are shown in Table 1.

[0144] Table 1

[0145] Carrier serial number Aperture / nm <![CDATA[Specific surface area / m 2 ·g -1 > Example 1 Carrier-1 7.9 354 Example 2 Carrier-2 6.4 477 Example 3 Carrier-3 4.8 524 Example 4 Carrier-4 4.2 652 Example 5 Carrier-5 6.5 456 Example 6 Carrier-6 6.0 518 Example 7 Carrier-7 6.0 584 Example 8 Carrier-8 4.5 692

[0146] As shown in Table 1, the specific surface area of ​​the maleic anhydride hydrogenation catalyst based on nickel-based ordered mesoporous silica materials provided in this invention ranges from 354 to 692 m² under different preparation conditions. 2 / g, a carrier with a pore size of 4.2–7.9 nm.

[0147] The catalysts obtained in the above examples and comparative examples catalyzed the hydrogenation of maleic anhydride to succinic anhydride under different reaction conditions. The reaction conditions, maleic anhydride conversion, succinic anhydride selectivity, γ-butyrolactone selectivity, and catalyst lifetime results are shown in Table 2.

[0148] Table 2

[0149]

[0150]

[0151] As can be seen from Table 2:

[0152] (1) As can be seen from Examples 1 to 10, the preparation method of maleic anhydride hydrogenation catalyst based on nickel-based ordered mesoporous silica-based material provided by the present invention can obtain a mesoporous maleic anhydride hydrogenation catalyst with a large specific surface area, which has good service life and high selectivity.

[0153] (2) It can be seen from the combined examples 1 and 11-12 that the amount of inorganic acid in example 11 is small, which leads to unstable pore structure and poor catalyst reactivity; the amount of inorganic acid in example 12 is large, which leads to more acidic sites on the catalyst surface and excessive reaction.

[0154] (3) It can be seen from the combined examples 1 and 13 that the solvent used in Example 13 is diethyl ether. Although diethyl ether is similar to tetrahydrofuran and can theoretically participate in the construction of the internal structure, it will volatilize during the heat preservation and stirring due to its low boiling point. Therefore, the internal pores of the prepared catalyst are not uniform, which greatly affects the reactivity.

[0155] (4) It can be seen from the combined results of Example 1 and Comparative Examples 1 to 3 that in Comparative Example 1, nickel was loaded onto the support by impregnation. Due to gravity, the active metal may be loaded more at the downward bend of the pores, while it is loaded relatively less in other places, resulting in uneven distribution of active metal. As a result, the conversion rate of maleic anhydride and the selectivity of succinic anhydride of the catalyst were reduced, and the selectivity of γ-butyrolactone was higher. The catalyst lifetime was only 2108h. In Comparative Example 2, the nickel loading was low, resulting in insufficient active sites and poor reactivity. In Comparative Example 3, the nickel loading was high, which caused the nickel metal to quickly agglomerate and block the pores, thus leading to rapid deactivation.

[0156] The applicant declares that the above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention fall within the protection and disclosure scope of the present invention.

Claims

1. The use of a maleic anhydride hydrogenation catalyst based on nickel-based ordered mesoporous silica materials, characterized in that, The maleic anhydride hydrogenation catalyst based on nickel-based ordered mesoporous silica material is used to catalyze the hydrogenation of maleic anhydride reaction solution to produce succinic anhydride. The maleic anhydride hydrogenation catalyst includes a nickel active component and a support, wherein the support is an ordered mesoporous silica-based material, and the nickel active component is loaded on the support in the form of atomic layers. The maleic anhydride hydrogenation catalyst based on nickel-based ordered mesoporous silica material is prepared by the following method, which includes the following steps: (1) In a hydrothermal reactor, at a temperature of 25°C, 3.32 g of surfactant polyoxypropylene-polyoxyethylene copolymer and 180 g of deionized water were mixed. 4.2 mL of 35 wt% hydrochloric acid was added to adjust the acidity, and the mixture was stirred continuously until the surfactant was completely dissolved. Then, 9.63 g of n-butanol was added and the mixture was subjected to a first heat treatment and stirring for 1.2 h. After the solution became clear, 20.83 g of tetraethyl orthosilicate was added and the mixture was subjected to a second heat treatment and stirring for 36 h. Then, the mixture was subjected to static aging at 90°C for 36 h, filtration, and drying at 120°C for 36 h to obtain the crude carrier product. (2) The crude carrier is first washed with ethanol three times and then washed with dilute hydrochloric acid three times, and then calcined at 500℃ for 12h to obtain carrier-1. (3) In an atomic layer deposition reactor at a temperature of 200°C, using tetramethylethylenediamine diacetylacetone nickel as a precursor, after pulse adsorption of the carrier-1 for 12s, the catalyst is sequentially subjected to a first nitrogen purging for 12s, ozone oxidation with a volume concentration of 7% for 10s, and a second nitrogen purging for 10s. The pulse adsorption, first nitrogen purging, ozone oxidation, and second nitrogen purging are repeated 10 times to obtain the maleic anhydride hydrogenation catalyst based on nickel-based ordered mesoporous silica material.

2. The use according to claim 1, characterized in that, The maleic anhydride hydrogenation catalyst is reduced in a hydrogen atmosphere before use, and the reduction temperature is 300~800℃.

3. The use according to claim 1, characterized in that, The mass concentration of the maleic anhydride reaction solution is 5-20%.

4. The use according to claim 1, characterized in that, The mass hourly space velocity (MSV) of the maleic anhydride reaction solution is 0.5–2 h⁻¹. -1 .

5. The use according to claim 1, characterized in that, The solvent tetrahydrofuran is used in the process of hydrogenating maleic anhydride reaction solution to produce succinic anhydride.

6. The use according to claim 1, characterized in that, The temperature for hydrogenating maleic anhydride reaction solution to produce succinic anhydride is 70~150℃.

7. The use according to claim 6, characterized in that, The temperature for hydrogenating maleic anhydride reaction solution to produce succinic anhydride is 90~120℃.

8. The use according to claim 1, characterized in that, The pressure at which the maleic anhydride reaction solution is hydrogenated to produce succinic anhydride is 1.0~3.0 MPa.

9. The use according to claim 8, characterized in that, The pressure at which the maleic anhydride reaction solution is hydrogenated to produce succinic anhydride is 2.0~3.0 MPa.

10. The use according to claim 1, characterized in that, The hydrogen-to-anhydride ratio for the hydrogenation of maleic anhydride reaction solution to produce succinic anhydride is 5:1 to 20:1.

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